Emerging Fluorinated MotifsSynthesis, Properties and Applications
A must-have resource for all the researchers working in the organofluorine and related fields This timely two-volume set uniquely focuses on emerging fluorinated motifs beyond R-CF3 and R-F, like R-CF2H, R-OCF3, R-SCF3 and R-SF5. It also offers descriptions of the properties, synthesis, and applications of these emerging fluorinated motifs in order to help readers design new chemical entities, while providing new interest for researchers in organofluorine chemistry and new tools for those in other areas. Emerging Fluorinated Motifs: Synthesis, Properties and Applications begins with a description of carbon-linked fluorine-containing groups that include monofluoromethyl and difluoromethyl groups. It then details combinations of heteroatoms, Oxygen, Sulfur, Selenium, Nitrogen, and Phosphorus with fluorine-containing groups, outlining subsections of the most popular current motifs. Fluoroalkyl ethers, thioethers, and the recent blossoming of the SF5 unit is covered. Other chapters look at: selenium-linked fluorine-containing motifs; construction of N?CF2H, N?CF3, N?CH2CF3 motifs; and the synthesis and applications of P¿Rf-containing molecules. -Focuses on the synthesis, properties, and applications of emerging fluorinated motifs -Covers carbon-linked fluorine-containing motifs, oxygen-linked fluorine-containing motifs, sulfur-linked fluorine-containing motifs, and more -Appeals to academic and industrial researchers working in organic chemistry, medicinal chemistry, food chemistry, and materials science -Edited by world-renowned experts in organofluorine chemistry Emerging Fluorinated Motifs is intended for academic research institutes, university libraries, researchers, graduate students, postdoctors, and researchers in the chemical industry.
Preface xiii Volume 1 Part I Carbon?Linked Fluorine?Containing Motifs 1 1 Difluoromethylation and Difluoroalkylation of (Hetero)Arenes: Access to Ar(Het)–CF2H and Ar(Het)–CF2R 3Yu?Lan Xiao and Xingang Zhang 1.1 Introduction 3 1.2 Difluoromethylation of (Hetero)aromatics 3 1.2.1 Transition?Metal?Mediated/Catalyzed Nucleophilic Difluoromethylation of (Hetero)aromatics 3 1.2.2 Catalytic Metal?Difluorocarbene?Involved Coupling (MeDIC) Reaction 10 1.2.3 Transition?Metal?Catalyzed Radical Difluoromethylation of (Hetero)aryl Metals/Halides and Beyond 11 1.2.4 Radical C?H Bond Difluoromethylation of (Hetero)aromatics 19 1.3 Difluoroalkylation of Aromatics 22 1.3.1 Transition?Metal?Catalyzed Phosphonyldifluoromethylation of (Hetero)aromatics 23 1.3.2 Transition?Metal?Catalyzed Difluoroacetylation of (Hetero)aromatics and Beyond 26 1.3.3 Other Catalytic Difluoroalkylations of (Hetero)aromatics 37 1.4 Outlook 39 References 42 2 Difluoromethylation and Difluoroalkylation of Aliphatic Unsaturated C=C, C?C, and ?N=C Bonds 47Sebastian Barata?Vallejo and Al Postigo 2.1 Introduction 47 2.2 Difluoromethylation of C?C Double Bonds 49 2.2.1 Intermolecular Difunctionalization of C?C Double Bonds 56 184.108.40.206 By Means of BrCF2P(O)(OR)2 56 220.127.116.11 By Means of Ph3P+CF2CO2? 59 18.104.22.168 By Means of HCF2R (R = CO2H, SO2NHNHBoc) 62 22.214.171.124 By Means of Selectfluor 65 126.96.36.199 By Means of BrCF2CO2Et 66 2.2.2 Difluoromethylation of C?C Double Bonds and Subsequent Cyclization 69 2.2.3 Difluoromethylation of C?C Double Bonds with Rearrangements 73 2.3 Difluoromethylation of Isocyanides 76 2.4 Difluoromethylation of Alkynes 79 2.5 Conclusion and Perspectives 82 References 85 3 Difluoromethylation and Difluoroalkylation in C(sp3) Centers and C?O, C?C, and C?N Bonds 89Qiqiang Xie and Jinbo Hu 3.1 Nucleophilic Difluoromethylation and Difluoroalkylation 89 3.1.1 By Means of XCF2PO(OEt)2 89 3.1.2 By Means of BrCF2CO2Et and BrCF2CH?CH2 89 3.1.3 By Means of Difluoromethylcadmium, Difluoromethylcopper, and Difluoromethylzinc Reagents 90 3.1.4 By Means of Difluoroalkylated Sulfone Reagents (XCF2SO2Ar) and Difluoromethylated Sulfoxides 90 3.1.5 By Means of Difluoroalkylated Silanes and Trifluoromethylsilane Reagents 94 3.1.6 By Means of Difluoromethyl Sulfoximine Reagent 96 3.1.7 Miscellaneous Reagents 96 3.2 Electrophilic Difluoromethylation and Difluoroalkylation 97 3.2.1 By Means of Difluorocarbene Reagents 97 3.2.2 By Means of CF3X (X ? H, I, TMS) Reagents 99 3.2.3 By Means of I(III)–CF2SO2Ph Reagent 100 3.2.4 By Means of S?((Phenylsulfonyl)difluoromethyl)thiophenium Salts 100 3.3 Free Radical Difluoromethylation and Difluoroalkylation 101 3.3.1 By Means of Iododifluoroacetates 101 3.3.2 By Means of CF2Br2, CF2BrCl, or TMSCF2Br 102 3.3.3 By Means of Phosphorus?containing Reagents 103 3.3.4 By Means of BrCF2CO2Et 104 3.3.5 By Means of Halodifluoroketone or ?Amide 107 3.3.6 By Means of HCF2I and PhCH2CF2I 107 3.3.7 By Means of HCF2SO2Cl and HCF2SO2Na or Zn(SO2CF2H)2 108 3.3.8 By Means of Difluoromethylated Sulfones, Sulfoximines, Thioethers, and Sulfonium Salts 109 3.3.9 By Means of TMSCF2CO2Et and ArCF2CO2H 112 References 112 4 Monofluoromethylation Reactions of Aliphatic Substrates and (Hetero)Arenes 119Qiqiang Xie and Jinbo Hu 4.1 Nucleophilic Monofluoromethylation 119 4.1.1 By Means of Fluoromalonates 119 4.1.2 By Means of Fluoromethyl Phenyl Sulfone 119 4.1.3 By Means of Fluorobis(phenylsulfonyl)methane 121 4.1.4 By Means of 2?Fluoro?2?Sulfonylketone 122 4.1.5 By Means of 2?Fluoro?1,3?benzodithiole?1,1,3,3?tetraoxide (FBDT) 123 4.1.6 By Means of TMSCF(SO2Ph)2 (TFBSM) 123 4.1.7 By Means of PhSO(NTBS)CH2F 123 4.1.8 By Means of CH2FI 124 4.1.9 By Means of Monofluoromethyl Phosphonium Salts 124 4.2 Electrophilic Monofluoromethylation 125 4.2.1 By Means of CH2FX (X = Cl, Br, I, OTf, OTs, OMs) 125 4.2.2 By Means of S?(monofluoromethyl)diarylsulfonium Tetrafluoroborate 125 4.2.3 By Means of Monofluoromethylsulfoxinium Salts 126 4.2.4 By Means of Monofluoromethylsulfonium Ylides 127 4.2.5 By Means of Monofluoromethyl Phosphonium Salts 127 4.3 Free Radical Monofluoromethylation 128 4.3.1 By Means of (PhSO2)2CFI 128 4.3.2 By Means of (H2FCSO2)2Zn (MFMS) 128 4.3.3 By Means of CH2FSO2Cl 128 4.3.4 By Means of PhSO(NTs)CH2F 129 4.3.5 By Means of Monofluoromethyl Sulfone 130 4.4 Transition?Metal?Catalyzed/Mediated Monofluoromethylation 130 4.4.1 By Means of CH2FI 130 4.4.2 By Means of PhSO2CHFI 131 4.4.3 By Means of CH2FBr 131 4.4.4 By Means of PTSO2CH2F 132 References 132 5 Synthesis of gem?Difluorocyclopropanes 135Dmitriy M. Volochnyuk and Oleksandr O. Grygorenko 5.1 Introduction 135 5.2 Intramolecular Wurtz (Freund) Reaction 140 5.3 Nucleophilic Fluorination of Pre?existing Ring System 140 5.4 Cyclopropanation of 1,1?Difluoroalkenes 142 5.5 Difluorocyclopropanation of Alkenes and Alkynes 143 5.5.1 Fragmentation of Trihalomethyl Anions CF2X? (X = Cl, Br) 145 5.5.2 Reduction of CF2Br2 with Zn or Other Reductants 146 5.5.3 Decarboxylative Difluorocarbene Generation 149 5.5.4 Difluorocarbene Generation by Nucleophilic Cleavage of a Carbene Precursor 153 5.5.5 Decomposition of CF3?substituted Organometallic Derivatives 164 5.5.6 Lewis Base?promoted Cleavage of the Ruppert–Prakash?type Reagents XCF2SiMe3 (X = F, Cl, Br) 169 5.5.7 Photodissociation of Difluorodiazirine 182 5.5.8 Thermal Decomposition of Hexafluoropropene Oxide 183 5.6 Michael?induced Ring Closure (MIRC) 183 5.7 Reactions at the Double Bond of gem?Difluorocyclopropenes 185 5.8 Conclusions 187 References 187 Part II Oxygen?Linked Fluorine?Containing Motifs 195 6 Indirect Construction of the OCF3 Motif 197Pingping Tang and Xiaohuan Jiang 6.1 Introduction 197 6.2 Fluorination of Trichloromethyl Ethers 197 6.3 Deoxyfluorination of Fluoroformates 198 6.4 Oxidative Fluorodesulfurization 198 6.5 Decarboxylative Fluorination 199 6.6 Direct Trifluoromethylation 200 6.7 Intramolecular OCF3 Migration 202 References 204 7 Reagents for Direct Trifluoromethoxylation 207Pingping Tang and Xiaohuan Jiang 7.1 Introduction 207 7.2 Trifluoromethyl Hypofluorite (FTM) 207 7.3 Chloroxytrifluoromethane 209 7.4 Bistrifluoromethyl Peroxide (BTMP) 210 7.5 Bis(trifluoromethyl) Trioxide 210 7.6 N?Trifluoromethoxy Benzimidazole 211 7.7 N?Trifluoromethoxypyridinium 213 7.8 N?Trifluoromethoxy Triazolium Salts 214 7.9 Trifluoromethyl Trifluoromethanesulfonate (TFMT) 215 7.10 Organometallic Trifluoromethoxides 217 7.11 Perfluoroalkylsulfurane 219 7.12 Perfluoroalkylsulfurane Oxide 219 7.13 2,4?Dinitro(trifluoromethoxy)benzene (DNTFB) 221 7.14 Trifluoromethyl Sulfonates (TFMS) 221 7.15 Trifluoromethyl Benzoate (TFBz) 222 References 223 8 Direct Trifluoromethoxylation of Aromatics and Heteroaromatics 225Johnny W. Lee, Katarzyna N. Lee, and Ming?Yu Ngai 8.1 Introduction 225 8.2 Direct Anionic Trifluoromethoxylation 226 8.3 Direct Radical Trifluoromethoxylation 239 8.4 Conclusion and Future Perspective 249 References 249 9 Direct Trifluoromethoxylation of Aliphatic Compounds 251Chaohuang Chen and Guosheng Liu 9.1 Direct Trifluoromethoxylation of Alkenes 251 9.1.1 Radical Trifluoromethoxylation of Alkenes 251 9.1.2 Pd(II)?Catalyzed Oxidative Trifluoromethoxylation of Alkenes 252 9.1.3 Silver(I)?catalyzed Trifluoromethoxylation of Alkenes 255 9.1.4 Direct Trifluoromethoxylation at sp3?Carbon Atoms 258 188.8.131.52 Trifluoromethoxylation of Alkyl Halides and Alkyl Triflates 258 184.108.40.206 Trifluoromethoxylation of Alkyl Alcohols and Alkyl Silanes 259 220.127.116.11 Trifluoromethoxylation of C–H Bonds 260 18.104.22.168 Nucleophilic Trifluoromethoxylation of Epoxides 262 9.2 Trifluoromethoxylation of ??Diazo Esters 263 9.3 Summary and Outlook 264 References 265 10 Extension to the Construction of ORf Motifs (OCF2H, OCFH2, OCH2CF3, OCFHCH3) 267Jin?Hong Lin and Ji?Chang Xiao 10.1 Introduction 267 10.2 Construction of the OCF2H Group 269 10.2.1 Insertion of Difluorocarbene into O?H Bond 269 10.2.2 Decarboxylative Fluorination 272 10.2.3 Direct Electrophilic Difluoromethylation 272 10.2.4 Difluoromethoxylation 273 10.2.5 Nucleophilic Fluorination 274 10.3 Construction of the OCFH2 Group 275 10.3.1 Monofluoromethylation 275 10.3.2 Fluorination 278 10.4 Construction of the OCH2CF3 Group 280 10.4.1 Trifluoroethoxylation 281 10.4.2 Trifluoroethylation 283 10.5 Construction of the OCFHCH3 Group 285 10.6 Conclusions and Perspectives 285 References 285 Volume 2 Preface xvii Part III Sulfur?Linked Fluorine?Containing Motifs 289 11 Indirect Trifluoromethylthiolation Methods 291Xiu?Hua Xu and Feng?Ling Qing 12 Reagents for Direct Trifluoromethylthiolation 309He Liu, Hangming Ge, and Qilong Shen 13 Trifluoromethylthiolation of Aromatic and Heteroaromatic Compounds 343Wenbin Yi, Zhidong Song, Jie Liu, Yasir Mumtaz, and Wei Zhang 14 Synthesis of Trifluoromethylthiolated Alkenes and Alkynes 373Matthew N. Hopkinson 15 Direct Trifluoromethylthiolation Toward C(sp3)–SCF3 Compounds 403Yumeng Liang, Dominique Cahard, and Norio Shibata 16 Extension to the SCF2H, SCH2F, and SCF2R Motifs (R = PO(OEt)2, CO2R, Rf) 449Tatiana Besset and Thomas Poisson 17 Synthesis and Applications of Fluorinated Sulfoxides (RSORF) and Sulfones (RSO2RF) 477Vinayak Krishnamurti, Colby Barrett, and G.K. Surya Prakash 18 Pentafluorosulfanylation of Aromatics and Heteroaromatics 551Petr Beier 19 Pentafluorosulfanylation of Aliphatic Substrates 571Günter Haufe 20 Extension to SF4CF3 and SF4FG Groups 611Peer Kirsch 21 Properties and Applications of Sulfur(VI) Fluorides 621Nicholas D. Ball 22 Construction of S–RF Sulfilimines and S–RF Sulfoximines 675Emmanuel Magnier Part IV Selenium?Linked Fluorine?Containing Motifs 691 23 When Fluorine Meets Selenium 693Thierry Billard and Fabien Toulgoat Part V Nitrogen?Linked Fluorine?Containing Motifs 723 24 Construction of N?CF2H, N?CF3, and N?CH2CF3 Motifs 725Thierry Milcent and Benoit Crousse Part VI Phosphorus?Linked Fluorine?Containing Motifs 763 25 Synthesis and Applications of P–Rf?Containing Molecules 765Fa?Guang Zhang and Jun?An Ma Index 809
Dominique Cahard, PhD, is Director of Research at the French National Center for Scientific Research, CNRS. His current research interests concern innovative methodologies for asymmetric synthesis of fluorinated molecules and the synthesis of fluorinated biomolecules. Jun-An Ma, PhD, is a Full Professor of organic chemistry at Tianjin University, P. R. of China. His current research efforts are focused on organofluorine chemistry, catalytic asymmetric synthesis, and the rational design & construction of biological molecules.
A must-have resource for all the researchers working in the organofluorine and related fields This timely two-volume set uniquely focuses on emerging fluorinated motifs beyond R-F and R-CF3, like R-CF2H, R-OCF3, R-SCF3 and R-SF5. It also offers descriptions of the properties, synthesis, and applications of these emerging fluorinated motifs in order to help readers design new chemical entities, while providing new interest for researchers in organofluorine chemistry and new tools for those in other areas. Emerging Fluorinated Motifs: Synthesis, Properties, and Applications begins with a description of carbon-linked fluorine-containing groups that include monofluoromethyl and difluoromethyl groups. It then details combinations of heteroatoms, Oxygen, Sulfur, Selenium, Nitrogen, and Phosphorus with fluorine-containing groups, outlining subsections of the most popular current motifs. Fluoroalkyl ethers, thioethers, and the recent blossoming of the SF5 unit is covered. Other chapters look at: selenium-linked fluorine-containing motifs; construction of N–CF2H, N–CF3, N–CH2CF3 motifs; and the synthesis and applications of P–Rf-containing molecules. Focuses on the synthesis, properties, and applications of emerging fluorinated motifs Covers carbon-linked fluorine-containing motifs, oxygen-linked fluorine-containing motifs, sulfur-linked fluorine-containing motifs, and more Appeals to academic and industrial researchers working in organic chemistry, medicinal chemistry, food chemistry, and materials science Edited by world-renowned experts in organofluorine chemistry Emerging Fluorinated Motifs is intended for academic research institutes, university libraries, researchers, graduate students, postdoctors, and researchers in the chemical industry.
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